Water-soluble fiber-reactive monoazo and disazo dyestuffs having a s-triazinylamino group and three fiber-reactive groups of the vinylsulfone series

ABSTRACT

Water-soluble dyes having fiber-reactive properties and conforming to the general formula (1) ##STR1## where F is the radical of a metal-free or heavy metal complex monoazo or disazo dye which contains at least one sulfo group, 
     n is 1 or 2, 
     Y is vinyl, β-sulfatoethyl, β-haloethyl, β-thiosulfatoethyl, β-phosphatoethyl or β-acetoxyethyl, 
     R.sup.α  is hydrogen or lower alkyl which may be substituted by carboxy, sulfo, cyano, hydroxyl or chlorine, 
     A is a group of the general formula (2a) or (2b) ##STR2##  where G is alkylene of 1 to 6 carbon atoms, alkylene of 2 to 6 carbon atoms which is interrupted by 1 or 2 hetero groups, or methyl-substituted cycloalkylene, 
     R is hydrogen, halogen, hydroxy, sulfato, cyano, carboxy, carbamoyl, lower carbalkoxy, lower alkanoylamino, substituted or unsubstituted benzoylamino or a group of the formula --SO 2  --Y 2   where Y 2  has one of the meanings of Y or is β-hydroxyethyl, 
     k is zero, 1 or 2, 
     k* is zero, 1, 2, 3, or 4, 
     X forms together with the N-atom the bivalent radical of a heterocyclic ring, 
     Y 1  has one of the meanings specified for Y, 
     W is hydrogen, methyl, sulfomethyl, carboxymethyl, substituted or unsubstituted lower alkyl, substituted or methyl-substituted cycloalkylene or substituted or unsubstituted phenyl, and 
     B has one of the meanings specified for A. 
     The dyes of the general formula (1) make it possible to obtain strong, fast dyeings and prints on carboxamido-containing and/or hydroxy-containing materials, in particular fiber materials, such as wool, synthetic polyamide and in particular cellulose fiber materials.

This application is a continuation of copending application Ser. No.07/461,115, filed on Jan. 4, 1990 now abandoned.

The invention relates to the field of fiber-reactive dyes.

The practice of dyeing with reactive dyes has in recent years led toincreased demands on the quality of the dyeings and the economics of thedyeing process. There consequently continues to be a demand for newreactive dyes which have improved properties, in particular applicationproperties. The dyeing of cotton by the cold pad-batch process thesedays requires reactive dyes which are sufficiently substantive at thelow dyeing temperature and which at the same time give good washing-offof the unfixed portions. Furthermore, they should be highly reactive, sothat only short batching times are required, and they should produce inparticular dyeings with high degrees of fixation. Known dyes, forexample those described in European Patent Specification No. 0,076,782B1, do not meet these requirements to a sufficient degree.

The present invention therefore has for its object to provide new,improved reactive dyes for the cold pad-batch process. They should inparticular give high degrees of fixation and high fiber-dye bondstabilities and show good washing-off of the unfixed portions.

This object is achieved by the present invention by the discovery ofdyes which conform to the general formula (1) ##STR3## where F is theradical of a metal-free or heavy metal complex monoazo or disazo dyewhich contains at least one sulfo group,

n is 1 or 2, preferably 1,

Y is vinyl, β-sulfatoethyl, β-haloethyl, such as β-chloroethyl,β-thiosulfatoethyl, β-phosphatoethyl or β-acetoxyethyl, preferably vinylor particularly preferably β-sulfatoethyl,

R.sup.α is hydrogen or straight-chain or branched alkyl of 1 to 4 carbonatoms which may be substituted by carboxy, sulfo, cyano, hydroxy orchlorine, preferably methyl, particularly preferably hydrogen,

A is a group of the general formula (2a) or (2b) ##STR4## where G isstraight-chain or branched alkylene of 1 to 6 carbon atoms, preferablyof 2 to 4 carbon atoms, in particular of 3 carbon atoms, alkylene of 2to 6 carbon atoms which is interrupted by 1 or 2 hetero groups, forexample by oxygen or the amino group --NH--, the alkylene moieties beingstraight-chain or branched and preferably having 2 or 3 carbon atoms, orunsubstituted or methyl-substituted cycloalkylene of 5 to 8 carbonatoms, preferably cyclohexylene,

R is hydrogen, chlorine, bromine or fluorine, hydroxy, sulfato, cyano,carboxy, carbamoyl, carbalkoxy of 2 to 5 carbon atoms, alkanoyloxy of 2to 5 carbon atoms, benzoylamino which may be substituted by 1 or 2substituents from the group consisting of sulfo, carboxy, methyl, ethyl,methoxy, ethoxy and chlorine, or a group of the general formula --SO₂--Y², where

Y² has one of the meanings specified above for Y or is β-hydroxyethyl,Y² and Y being identical or different,

k is zero, 1 or 2,

k* is zero, 1, 2, 3 or 4,

X is together with the N-atom the bivalent radical of a heterocyclicring containing of 1 or 2 alkylene groups of 1 to 5 carbon atoms with orwithout 1 or 2 hetero atoms, such as nitrogen and oxygen atoms, forexample piperazin-1,4-ylene or piperidinylene,

Y¹ has one of the meanings specified above for Y, Y¹ being identical toor different from Y, preferably being vinyl, β-chloroethyl orβ-sulfatoethyl, and

W is hydrogen, methyl, sulfomethyl, carboxymethyl, straight-chain orbranched alkyl of 2 to 6 carbon atoms, preferably of 2 to 4 carbonatoms, which may be substituted by 1 or 2 substituents from the groupconsisting of methoxy, ethoxy, carboxy, sulfo, hydroxy and halogen, suchas chlorine and bromine, unsubstituted on methyl-substitutedcycloalkylene of 5 to 8 carbon atoms, such as cyclohexylene, or phenylwhich may be substituted by substituents from the group consisting ofalkyl of 1 to 4 carbon atoms, such as methyl and ethyl, alkoxy of 1 to 4carbon atoms, such as methoxy and ethoxy, carboxy, sulfo and halogen,such as chlorine, and

B has one of the meanings specified for A, A and B having meaningsidentical to or different from each other.

Heavy metal monoazo and disazo dyes from which F is derived are inparticular copper, nickel, cobalt and chromium complex dyes. The dyeradical F preferably contains 2 to 6, in particular 2 to 4, sulfogroups.

Besides hydrogen and methyl the meanings of R.sup.α are in particularethyl, 1-propyl, 2-propyl, 1-butyl, 2-methyl-1-propyl, tert-butyl,carboxymethyl, sulfomethyl, β-sulfoethyl, β-cyanoethyl, β-chloropropyland β-hydroxyethyl.

Preferably, W is methyl or ethyl or particularly preferably hydrogen.

The substituents "sulfo", "carboxy", "phosphato", "thiosulfato" and"sulfato" include not only their acid forms but also their salt forms.Accordingly, sulfo groups are groups conforming to the general formula--SO₃ M, carboxy groups are groups conforming to the general formula--COOM, phosphato groups are groups conforming to the general formula--OPO₃ M₂, thiosulfato groups are groups conforming to the generalformula --S--SO₃ M and sulfato groups are groups conforming to thegeneral formula --OSO₃ M, in each of which M is hydrogen or an alkalimetal, such as sodium, potassium or lithium.

Dyes conforming to the general formula (1) according to the inventionare in particular those monoazo and disazo dyes, and the heavy metalcomplexes derived therefrom, conforming to the general formulae (3a) or(3b)

    (Y--SO.sub.2 --X.sup.1).sub.n --D--N=N--E--N=N).sub.v K--Z (3a)

    Z--D--N=N--E--N=N).sub.v K--X.sup.1 --SO.sub.2 --Y         (3b)

where

Y and n are each as defined above,

X¹ is a direct bond or a bridge member, for example an alkylene group of1 to 4 carbon atoms or the bivalent radical of an alkanoylamido group of2 to 5 carbon atoms,

n is 1 or 2, preferably 1,

Z is a group of the general formula (4) ##STR5## where R.sup.α, A and Bare each as defined above, D is the radical of a benzene or naphthaleneseries diazo component customary in azo chemistry which may containsubstituents customary for azo dyes, for example sulfo, carboxy,hydroxy, amino, methyl, ethyl, methoxy, ethoxy, substituted orunsubstituted alkanoylamino of 2 to 4 carbon atoms, substituted orunsubstituted benzoylamino or halogen,

K is the radical of a benzene, naphthalene, pyrazolone,6-hydroxy-2-pyridone or acetoacetarylamide series coupling componentcustomary in azo chemistry which may contain substituents customary forazo dyes, for example hydroxy, sulfo, carboxy, amino, methyl, ethyl,methoxy, ethoxy, substituted or unsubstituted alkanoylamino of 2 to 4carbon atoms, substituted or unsubstituted benzoylamino or halogen,

E is the radical of a benzene or naphthalene series middle componentcustomary in disazo dyes which may be substituted by substituentscustomary for azo dyes, for example sulfo, carboxy, hydroxy, methyl,ethyl, methoxy, ethoxy, substituted or unsubstituted alkanoylamino of 2to 4 carbon atoms, substituted or unsubstituted ureido, substituted orunsubstituted benzoylamino or halogen,

v is zero or 1, and

D, E and K together contain at least one, preferably at least two sulfogroups, preferably 3 or 4 sulfo groups.

Of the dyes according to the invention, notable dyes are in particularthose which conform to the general formulae (5a), (5b), (5c) and (5d)##STR6## where Y, M, n, v and Z are each as defined above,

X¹ is as defined above, preferably a group of the formula --(CH₂)₃--CO--NH-- or particularly preferably a direct bond,

X² has one of the meanings specified for X¹ and preferably is a group ofthe formula --NH--CO--(CH₂)₃ -- or particularly preferably a directbond,

D⁰ is a radical of the general formula (6a), (6b) or (6c) ##STR7## whereR¹ in the one D⁰ is one or two groups of the above-mentioned andabove-defined general formula Y--SO₂ --X¹ --, where --X¹ -- has one ofthe abovementioned meanings, in particular a preferred meaning, and R¹in the other D⁰ is a radical Z of the general formula (4),

R² is hydrogen, methyl, ethyl, methoxy, ethoxy, alkanoyl of 2 to 5carbon atoms, such as acetyl or propionyl, cyano, carboxy, sulfo,alkoxycarbonyl of 2 to 5 carbon atoms, carbamoyl, N-(C₁ -C₄-alkyl)carbamoyl, fluorine, chlorine, bromine or trifluoromethyl,

R³ is hydrogen, methyl, ethyl, methoxy, ethoxy, cyano, carboxy, sulfo,alkanoylamino of 2 to 5 carbon atoms, such as acetylamino,alkoxycarbonyl of 2 to 5 carbon atoms, carbamoyl, N-(C₁ -C₄-alkyl)carbamoyl, fluroine, chlorine, nitro, sulfamoyl,N-(C₁ -C₄-alkyl)sulfamoyl, alkylsulfonyl of 1 to 4 carbon atoms, phenylsulfonylor phenoxy,

p is zero, 1 or 2 (if zero, the group being hydrogen) and

M is as defined above,

D¹ is phenylene with the abovementioned and above-defined substituentsR² and R³ or is naphthylene which may be substituted by 1 or 2 sulfogroups,

E¹ is a radical of the general formula (7a), (7b), (7c) or (7d) ##STR8##where R², R³, M and p are each as defined above,

R⁴ is hydrogen, alkyl of 1 to 4 carbon atoms, such as methyl or ethyl,alkoxy of 1 to 4 carbon atoms such as methoxy or ethoxy, chlorine,alkanoylamino of 2 to 5 carbon atoms, such as acetylamino orpropionylamino, benzoylamino, ureido, N'-phenylureido, N'-alkylureidohaving 1 to 4 carbon atoms in the alkyl moiety, phenylsulfonyl oralkylphenylsulfonyl of 1 to 4 carbon atoms,

m is 1 or 2, and

R⁸ is hydrogen, alkyl of 1 to 4 carbon atoms, such as methyl, cyano,carboxy, carbalkoxy of 2 to 5 carbon atoms, carbamoyl or phenyl, butpreferably is methyl, carboxy or carbalkoxy of 2 to 5 carbon atoms, suchas carbomethoxy or carboethoxy,

--K*--Z is a radical of the general formula (8a), (8b), (8c), (8d), (8e)or (8f) ##STR9## where R¹, R², R³, Z, p and M are each as defined aboveand the hydroxy group in the formula (8b) is ortho to the free bondattached to the azo group,

V is a phenylene radical which contains the abovementioned andabove-defined radicals R² and R³ or is a naphthylene radical which maybe substituted by 1 or 2 sulfo groups,

R⁵ is a direct bond or a radical of the formula --NH--CO-phenylene,--NH--CO--NH-phenylene, --N(CH₃)--CO-phenylene or--N(CH₃)--CO--NH-phenylene,

R⁶ is hydrogen, alkyl of 1 to 4 carbon atoms, such as methyl or ethyl,alkoxy of 1 to 4 carbon atoms, such as methoxy or ethoxy, bromine,chlorine or alkanoylamino of 2 to 7 carbon atoms, such as acetylaminoand propionylamino,

R⁷ is hydrogen, alkyl of 1 to 4 carbon atoms, such as methyl or ethyl,alkoxy of 1 to 4 carbon atoms, such as methoxy or ethoxy, chlorine oralkanoylamino of 2 to 7 carbon atoms, such as acetylamino orpropionylamino, ureido or phenylureido,

R⁸ is as defined above,

R^(x) is hydrogen, alkyl of 1 to 4 carbon atoms, such as methyl, oralkyl substituted by alkoxy of 1 to 4 carbon atoms, such as methoxy, orby cyano,

R^(y) is hydrogen, sulfo, sulfoalkyl having an alkylene moiety of 1 to 4carbon atoms, such as sulfomethyl, cyano or carbamoyl, and

R^(z) is alkylene of 1 to 6 carbon atoms, preferably of 1 to 4 carbonatoms, phenylene, which may be substituted by substituents from thegroup consisting of methyl, ethyl, chlorine, carboxy and sulfo, oralkylenephenylene having 2 to 4 carbon atoms in the alkylene moiety,

D* is phenylene, which may be substituted by 1 or 2 substituents fromthe group consisting of hydrogen, methyl, ethyl, methoxy, bromine,chlorine, carboxy and sulfo, or naphthylene, which may be substituted by1 or 2 sulfo groups,

K¹ is a radical of the general formula (9a), (9b) or (9c) ##STR10##where M, p, V, R², R³ and R⁸ are each as defined above and the hydroxygroup in the formula (9a) is ortho to the free bond attached to the azogroup,

D² is a benzene radical, which may be substituted by 1 or 2 substituentsfrom the group consisting of methyl, ethyl, methoxy, ethoxy, bromine,chlorine, carboxy or sulfo, or a naphthalene radical, which may besubstituted by a sulfo group, and

K² is a radical of the general formula (10a) or (10b) ##STR11## where M,p, R², R³ and R⁸ are each as defined above.

In the dyes according to the invention, the radical Z of the generalformula (4) is preferably a radical of the general formula (4A)##STR12## where each a is 2 or preferably 3 and Y¹ is as defined above,each Y¹ preferably being vinyl, β-chloroethyl or β-sulfatoethyl.

Preference is accordingly given in particular to dyes of the generalformula (1) and of the general formulae (3a), (3b), (5a), (5b), (5c) and(5d), where R.sup.α is hydrogen and A and B are identical to each other,each being a radical of the general formula --NH--(CH₂)_(a) --SO₂ --Y¹,wherein a and Y¹ are each as defined, in particular preferred, above.

Of the dyes according to the invention, notable ones are further thoseconforming to the following general formulae (11a) to (11n): ##STR13##In these formulae the symbols have the following meanings: M is asdefined above, preferably hydrogen or in particular sodium, potassium orlithium,

D³ is a phenyl or 2-naphthyl radical which is substituted by a group ofthe above-defined general formula --SO₂ --Y and which may additionallybe substituted by substituents as per groups R² and R³ of the abovedefinition, D³ preferably being 4-(β-sulfatoethylsulfonyl)phenyl,4-(vinylsulfonyl)phenyl, 3-(β-sulfatoethylsulfonyl)phenyl,3-(vinylsulfonyl)-phenyl, 2-sulfo-4-(β-sulfatoethylsulfonyl)phenyl,2-sulfo-4-(vinylsulfonyl)phenyl,4-methoxy-3-(β-sulfatoethylsulfonyl)phenyl,4-methoxy-3-(vinylsulfonyl)phenyl,1-sulfo-6-(β-sulfatoethylsulfonyl)-2-naphthyl or1-sulfo-6-(vinylsulfonyl)-2-naphthyl,

Z¹ is a group of the general formula (4a) ##STR14## where A and B areeach as defined, in particular preferred, above, R* is hydrogen ormethyl,

R.sup.β is methyl, acetylamino or ureido,

R.sup.γ is hydrogen, cyano or carbamoyl,

r is 2 or 3,

D⁴ is a group of the general formula (12) ##STR15## where M and Z¹ areeach as defined above and Z¹ --HN-- is bonded to the benzene nucleuseither para to the free bond attached to the azo group or para to thesulfo group,

R⁹ is methyl or carboxy,

Y is as defined above, preferably vinyl or in particular β-sulfatoethyl,

R⁺ is a direct bond or the group --NH--,

D⁵ is in the one instance a radical D⁴ of the abovementioned meaning andin the other a radical D³ of the abovementioned meaning,

R¹⁰ is hydrogen, methyl or methoxy, and

the sulfo group --SO₃ M in the formulae (11k) and (11m) is bonded to thenaphthalene in the 5-, 6- or 8-position.

Of these compounds, notable ones are in particular those conforming tothe general formula (11a) in which M is as defined, in particularpreferred, above and D³ is phenyl substituted para to the azo group by agroup of the formula --SO₂ -- Y, where Y is as defined above, preferablyvinyl or in particular β-sulfatoethyl, or D³ is 1-sulfo-2-naphthylsubstituted in the 6-position by --SO₂ --Y, where Y is as defined above,preferably vinyl or in particular β-sulfatoethyl, and in which Z¹ is aradical of the general formula (4B) ##STR16## where a is 2 or preferably3.

Of the compounds of the general formula (11j) the preferred compound isin particular the compound of the formula (11p) ##STR17## where Y and Mare each as defined, in particular preferred, above and Z¹ is a radicalof the abovementioned and above-defined formula (4B).

Of the abovementioned compounds, interesting ones are furthermore thoseof the general formula (11b) in which in particular D³ is phenylsubstituted para to the azo group by a methoxy group and meta to the azogroup by --SO₂ --Y, where Y is as defined above, preferably vinyl or inparticular β-sulfatoethyl, M is as defined, in particular preferred,above, R* is hydrogen and Z¹ is a group of the formula (4C) ##STR18##where M and a are each as defined above.

The present invention further relates to processes for preparing thedyes according to the invention. For example, they can be preparedaccording to the invention in the manner of known processes forsynthesizing azo dyes or heavy metal complexes thereof by converting dyeintermediates familiar to the person skilled in the art, at least one ofthese dye intermediates containing a fiber-reactive grouping of thegeneral formula (4) and at least one of the intermediates containing an--SO₂ --Y and/or --SO₂ --Y² group. For instance, monoazo and disazo dyesof the general formula (1) can be synthesized by reacting their diazoand coupling components, which each contain a fiber-reactive group ofthe general formula (4) or the formula --SO₂ --Y or --SO₂ --Y², by theusual method of diazotization and coupling. If disazo dyes are to besynthesized, the diazo or coupling component may already contain thesecond azo group. Diazo components usable according to the invention arethe aromatic carbocyclic and heterocyclic amino compounds which arecustomary for fiber-reactive azo dyes and which may contain thefiber-reactive group of the general formula (4) or --SO₂ --Y or --SO₂--Y², and coupling components usable according to the invention arethose coupling components customary for the synthesis of fiber-reactiveazo dyes, for example of the naphthol, aniline, naphthylamine,aminonaphthol, pyrazolone or pyridone series, which contain thefiber-reactive group of the general formula --SO₂ --Y or --SO₂ --Y² orof the general formula (4). Such diazo compounds are for examplecompounds which conform to the general formula D⁰ --NH₂ or D*--Z or (Y²--SO₂ --X₁)_(n) --D¹ -- or (Y² --SO₂ --X¹)_(n) --D² (OH)-- where D⁰, D*,Z, Y², X¹, n, D¹ and D² are each as defined above, and such couplingcomponents are for example the following compounds of the generalformulae (13a) to (13d) and (14a) to (14c): ##STR19## where Z, Y², V,R⁵, M, p, R², R³, R⁸, R^(x), R^(y) and R^(z) are each as defined above.

Further diazo components which according to the invention can be usedfor synthesizing of the dyes of the general formula (1) are for examplediamino compounds of the general formula H₂ N--D--NH₂ or H₂ N--D*--NH₂,where D and D* are each as defined above, or their monoacylaminoderivatives (in which the acyl group acts as a customary protectivegroup to prevent diazotization of the second amino group and ishydrolytically eliminatable in the conventional manner afterdiazotization and coupling). The aminoazo compounds obtainable withthese diazo components can then be reacted according to the inventionwith a cyanuric halide or with a compound of the general formula Z¹--Hal, where Z¹ is as defined above and Hal is halogen, such asfluorine, bromine or chlorine, by the known methods of reacting aminocompounds or aminoazo compounds with halotriazine derivatives.

The diazotization and coupling reactions are carried out in aconventional manner; for instance the diazotization in general at atemperature of between -5° C. and +15° C. and at a pH below 2 by meansof a strong acid and an alkali metal nitrite in a preferably aqueousmedium and the coupling reaction in general at a pH between 1.5 and 4.5in the case of an amino-containing coupling component and at a pHbetween 3 and 7.5 in the case of a hydroxy-containing coupling componentand at a temperature of between 0° and 25° C., again preferably in anaqueous medium.

The dyes according to the invention can likewise be prepared accordingto the invention by reacting a cyanuric halide, such as cyanuricfluoride, cyanuric bromide or cyanuric chloride, with a compound of thegeneral formula (15) ##STR20## where F, Y, R.sup.α and n are each asdefined above, and one or two amino compounds of the general formula(16)

    H.sub.2 N--A                                               (16)

where A has one of the abovementioned meanings, including anothermeaning as per the radical B, in any desired order. For instance, firstan amino compound of the general formula (15) can be reacted with acyanuric halide, preferably cyanuric chloride or cyanuric fluoride, togive a dihalotriazinylamino compound of the general formula (17)##STR21## where Hal is halogen, preferably chlorine or fluorine, and F,Y, R.sup.α and n are each as defined above, and this product isconverted by reaction with one or two amino compounds of the generalformula (16) in an equivalent amount into the final dye (1), or first anamino compound of the general formula (16) is reacted with a cyanurichalide to give a halotriazinylamino compound of the general formula(18a) or (18b) ##STR22## where Hal, A and B are each as defined aboveand this product is converted in an equivalent amount with a compound ofthe general formula (15) into the final dye (1). The condensationreactions between the cyanuric halide or the halotriazinylaminocompounds (17) and (18) with the amino compounds (15) and/or (16) can becarried out in the usual manner of the reaction of a cyanuric halide orhalotriazinylamino compound with an amino compound, for instance in anorganic or preferably aqueous organic medium, particularly preferably inan aqueous medium in the presence of an acid-binding agent, such as analkali metal or alkaline earth metal carbonate, an alkali metal oralkaline earth metal bicarbonate or hydroxide or an alkali metalacetate, the alkali and alkaline earth metals preferably being sodium,potassium or calcium. Acid-binding agents also include tertiary amines,for example pyridine, triethylamine or quinoline. If these condensationreactions are carried out in an organic or aqueous organic medium, theorganic solvent (content) is acetone, dioxane or dimethylformamide.

The condensation reactions between the cyanuric halide and the aminocompounds generally take place at a temperature between -10° C. and +70°C., preferably between -5° C. and +30° C., and at a pH between 1.5 and12, preferably between 4.5 and 8. The reaction of the halotriazinylaminocompounds of the general formulae (17) or (18) with an amino compound ofthe general formula (15) or (16) is carried out for example at atemperature between 0° and 70° C., preferably between 10° and 50° C.,and at a pH between 2 and 8, preferably between 4 and 7.

With the condensation reactions care must be taken to ensure that thefiber-reactive groupings are not damaged in the alkaline range.

Those dyes according to the invention where --SO₂ --Y isβ-sulfatoethylsulfonyl or β-phosphatoethylsulfonyl can also be preparedaccording to the invention by reacting a dye of the general formula (1)of the same structure except that one or more of the formulae Y, Y¹ andY² is β-hydroxyethyl in a known manner with a sulfating agent orphosphating agent, such as concentrated sulfuric acid, SO₃ -containingsulfuric acid, aqueous concentrated phosphoric acid or polyphosphoricacid, sulfation generally taking place at a temperature between 10° C.and 25° C. and phosphation at a temperature between 20° and 100° C.

The starting dyes with the β-hydroxyethylsulfonyl groups aresynthesizable similarly to the above directions for the preparations ofthe dyes according to the invention by either using corresponding dyeintermediates which contain these β-hydroxyethylsulfonyl groups orreacting an amino dye of the general formula (15) and an amino compoundof the general formula (16) where however Y is β-hydroxyethyl with acyanuric halide under the above reaction conditions.

In the synthesis of heavy metal complex azo dyes according to theinvention, for example those conforming to the general formulae (5d),the starting materials are in general those azo compounds free of heavymetal which contain in the coupling component an attached phenolic ornaphtholic hydroxy group ortho or vicinally to the azo group and whosediazo component radical contains attached ortho to the azo group ahydrogen atom or a hydroxy group or a lower alkoxy group, such asmethoxy, and which in addition contain an attached acylamino radical,such as an acetylamino conforming to the general formula--N(R.sup.α)-acyl, where acyl is the acyl radical of an organic acid,such as a lower alkanecarboxylic acid, and R.sup.α is as defined above,for example a starting compound conforming to the general formula (20)##STR23## where R¹, R², R³, D², K², K^(*), v and R.sup.α are each asdefined above and R^(k) is hydrogen or a hydroxy or methoxy groupattached to D² ortho to the azo group, and this acylamino-containingstarting azo compound is reacted by known and customary methods with aheavy metal donor, such as a heavy metal salt, or else, if a coppercomplex azo dye is to be formed, is subjected to a conventionaloxidative or dealkylating coppering reaction. The resultingacylamino-containing heavy metal complex azo compounds can then bereacted by known methods, with hydrolysis of the acylamino group to anamino group, with a cyanuric halide and an amino compound conforming tothe general formula (16) to give the dyes of the general formula (1)according to the invention.

Dyes conforming to the general formula (1) according to the inventionwhere one or more of Y, Y¹ and Y² are vinyl can also be preparedaccording to the invention from dyes conforming to the general formula(1) where at least one of Y, Y¹ and Y² is β-sulfatoethyl or β-haloethylby converting the β-sulfatoethyl or β-haloethyl group by treatment withan aqueous alkali, for example sodium bicarbonate or sodium hydroxide,for instance in an aqueous medium at a temperature of 50° to 60° C. anda pH of 9 to 11, into a vinyl group.

The starting compounds of the general formula (16) are known for examplefrom German Patent Specification 2,614,550 and from European PatentSpecification No. 0,076,782 mentioned at the beginning. Compounds notexplicitly described therein can be prepared in a similar mannerfamiliar to the chemist, for example as per the relevant direction inGerman Patent Specification No. 887,505.

Aromatic amines conforming to the general formula (Y--SO₂ --X¹ --)_(n)--D--NH₂ for use as diazo components in the monoazo and disazo dyesaccording to the invention and for use as starting compounds forsynthesizing these dyes are for example 4-VS-aniline (where VS is hereand hereinafter a group of the general formula --SO₂ --Y² where Y² is asdefined above), 3-VS-aniline, 2-bromo-4-VS-aniline,2-sulfo-5-VS-aniline, 2-sulfo-4-VS-aniline, 2-methoxy-5-VS-aniline,2-methoxy-5-methyl-4-VS-aniline, 2,5-dimethoxy-4-VS-aniline,2-hydroxy-5-VS-aniline, 4-chloro-3-VS-aniline, 2-chloro-5-VS-aniline,3,4-di-VS-aniline, 2,5-di-VS-aniline,4-(β-sulfatoethylamino)-3-VS-aniline,2-(β-sulfatoethylamino)-5-VS-aniline,4-(β-succinylamidoethylamido)-3-VS-aniline,4-(3'-VS-benzoylamido)aniline, 3-(3'-VS-benzoylamido)aniline,6-VS-2-naphthylamine, 8-VS-2-naphthylamine,1-sulfo-6-VS-2-naphthylamine, 6-sulfo-8-VS-2-naphthylamine,6-sulfo-8-VS-1-hydroxy-2-naphthylamine, 2-amino-4,4'-di-VS-diphenyl,2-sulfo-5-[γ-(β'-chloroethylsulfonyl)butyryl-amino]aniline,2-sulfo-5-[γ-(vinylsulfonyl)butyrylamino]-aniline,2-sulfo-4-[γ-(β'-chloroethylsulfonyl)butyryl-amino]aniline and2-sulfo-4-[γ-(vinylsulfonyl)butyryl-amino]aniline.

Starting compounds conforming to the general formula H₂ N--D--NH₂ or H₂N--D*--NH₂ are for example 1,4-phenylenediamine,1,4-phenylenediamine-2-sulfonic acid, 1,4-phenylenediamine-2-carboxylicacid, 1,4-diaminonaphthalene-2-sulfonic acid,2,6-diaminonaphthalene-8-sulfonic acid,2,6-diaminonaphthalene-4,8-disulfonic acid, 1,3-phenylenediamine,1,3-phenylenediamine-4-sulfonic acid,1,3-phenylenediamine-4,6-disulfonic acid,1,4-phenylenediamine-2,6-disulfonic acid,1,4-phenylenediamine-2,5-disulfonic acid,1,4-diaminonaphthalene-6-sulfonic acid, 4,4'-diaminobiphenyl-3-sulfonicacid and 4,4'-diaminostilbene-2,2'-disulfonic acid.

Starting compounds conforming to the general formula H--E--NH₂ or H--E¹--NH₂ which can be used for synthesizing the diazo dyes according to theinvention and which act not only as coupling components but subsequentlyto the coupling as diazo components are for example aniline,3-methylaniline, 2,5-dimethylaniline, 2,5-dimethoxyaniline,3-methoxyaniline, 3-acetylaminoaniline, 3-propionylaminoaniline,3-butyrylaminoaniline, 3-benzoylaminoaniline, 3-ureidoaniline,2-methyl-5-acetylaminoaniline, 2-methoxy-5-acetylaminoaniline,2-methoxy-5-methylaniline, 1-aminonaphthalene-6-sulfonic acid,1-aminonaphthalene-7-sulfonic acid, 2-sulfo-5-acetylaminoaniline,2-amino-5-naphthol-7-sulfonic acid, 2-amino-8-naphthol-6-sulfonic acid,2-(4'-aminobenzoylamino)-5-naphthol-7-sulfonic acid,1-(4'-amino-2-sulfophenyl)-3-methyl- or -3-carboxy-5-pyrazolone andN-(3-sulfo-4-amino)acetoacetanilide.

Starting compounds for use as coupling components conforming to thegeneral formula H--K¹ --X² --SO₂ --Y² or H--K--X¹ --SO₂ --Y² forsynthesizing the dyes according to the invention are for example1-[4'-(β-sulfatoethylsulfonyl)phenyl]-3-methyl-5-pyrazolone,1-[4'-(vinylsulfonyl)phenyl]-3-methyl-5-pyrazolone,1-[4'-(vinylsulfonyl)phenyl]-3-carboxy-5-pyrazolone,1-[3'-(β-chloroethylsulfonyl)benzoylamino]-3,6-disulfo-8-naphthol,1-[3'-(vinylsulfonyl)benzoylamino]-3,6-disulfo-8-naphthol,1-[3'-(vinylsulfonyl)benzoylamino]-4,6-disulfo-8-naphthol,1-[3'-(β-sulfatoethylsulfonyl)benzoylamino]-4,6-disulfo-8-naphthol,2-[3'-(β-chloroethylsulfonyl)benzoylamino]-6-sulfo-8-naphthol,2-[3'-(vinylsulfonyl)benzoylamino]-6-sulfo-8-naphthol,3-[3'-(β-chloroethylsulfonyl)benzoylamino]-6-sulfo-8-naphthol,3-[3'-(vinylsulfonyl)benzoylamino]-6-sulfo-8-naphthol,2-[N-methyl-N-(β-sulfatoethylsulfonyl)amino]-6-sulfo-8-naphthol,3-[N-methyl-N-(β -sulfatoethylsulfonyl)amino]-6-sulfo-8-naphthol,2-[N-ethyl-N-(β-sulfatoethylsulfonyl)amino]-6-sulfo-8-naphthol,1-[N'-(3'-β-chloroethylsulfonylphenyl)ureido]-3,6-disulfo-8-naphthol,1-[N'-(3'-vinylsulfonylphenyl)ureido]-3,6-disulfo-8-naphthol,1-[N'-(3'-vinylsulfonylpropyl)ureido]-3,6-disulfo-8-naphthol,1-[N'-(3'-β-chloroethylsulfonylphenyl)ureido]-4,6-disulfo-8-naphthol,1[N'-(3'-vinylsulfonylphenyl)ureido]-4,6-disulfo-8-naphthol,1-[N'(3'-β-chloroethylsulfonylpropyl)ureido]-4,6-disulfo-8-naphthol,2-[N'-(3'-β-sulfatoethylsulfonylphenyl)ureido]-6-sulfo-8-naphthol,2-[N'-(3'-β-chloroethylsulfonylpropyl)ureido]-6-sulfo-8-naphthol,3-[N'-(3'-β-chloroethylsulfonylphenyl)ureido]-6-sulfo-8-naphthol,3-[N'-(3'-vinylsulfonylpropyl)ureido]-6-sulfo-8-naphthol,2-sulfo-5-[N'-(3"-β-chloroethylsulfonyl)phenyl]-ureidoaniline and3-[N'-(3"-β-sulfatoethylsulfonyl)phenyl]ureidoaniline.

Coupling components conforming to the general formula H--K--NHR.sup.α orH--K*--NHR.sup.α for use in the synthesis of azo dyes according to theinvention where the fiber-reactive radical of the general formula (4) ispresent in the coupling component into whose amino group --NHR.sup.αthis fiber-reactive radical can subsequently be introduced are forexample aniline, 3-methylaniline, 2,5-dimethylaniline,2,5-dimethoxyaniline, 3-methoxyaniline, 3-acetylaminoaniline,3-propionylamionoaniline, 3-butyrylaminoaniline, 3-benzoylaminoaniline,3-ureidoaniline, 2-methyl-5-acetylaminoaniline,2-methoxy-5-acetylaminoaniline, 2-methoxy-5-methylaniline,1-aminonaphthalene-6-sulfonic acid, 1-amino-7-sulfonic acid,1-aminonaphthalene-8-sulfonic acid, 2-sulfo-5-acetylaminoaniline,2-amino-5-naphthol-7-sulfonic acid, 2-amino-8-naphthol-6-sulfonic acid,2-(4'-aminobenzoylamino)-5-naphthol-7-sulfonic acid, 1-(4'-amino- or-acetylamino-2-sulfophenyl)-3-methyl- or -3-carboxy-5-pyrazolone,N-(3-sulfo-4-amino)acetoacetanilide, 1-amino-8-naphthol-3,6- or-4,6-disulfonic acid, 1-( 3'- or1-(4'-aminobenzoyl)amino-8-naphthol-3,6- or -4,6-disulfonic acid,1-acetylamino-8-naphthol-3,6- or -4,6-disulfonic acid,2-acetylamino-5-naphthol-7-sulfonic acid,2-acetylamino-8-naphthol-6-sulfonic acid,3-acetylamino-8-naphthol-6-sulfonic acid,3-(N-methylamino)-8-naphthol-6-sulfonic acid, 1-(3'-amino- or-acetylamino-6'-sulfophenyl)-3-methyl- or -3-carboxy-5-pyrazolone,2-(N-methyl-N-acetylamino)- or -methylamino-5-naphthol-7-sulfonic acid,N-methylaniline and N-propyl-m-toluidine.

Starting compounds conforming to the general formula (16) are forexample γ-(β'-chloroethylsulfonyl)propylamine,γ-(β'-sulfatoethylsulfonyl)propylamine,γ-(β'-hydroxyethylsulfonyl)propylamine, vinylsulfonyl)-propylamine,N-ethyl-β-(β'-chloroethylsulfonyl)ethylamine,N-ethyl-γ-(β'-chloroethylsulfonyl)propylamine,N-ethyl-γ-(β'-sulfatoethylsulfonyl)propylamine,N-ethyl-γ-(β'-hydroxyethylsulfonyl)propylamine,N-ethyl-γ-(vinylsulfonyl)propylamine,bis-γ-[(β-chloroethylsulfonyl)propyl]amine,bis-γ-[(β-hydroxyethylsulfonyl)propyl]amine,β-hydroxy-γ-(β'-chloroethylsulfonyl)propylamine, β,γ-di-(β'-chloroethylsulfonyl)propylamine,β-acetoxy-γ-(β'-acetoxyethylsulfonyl)propylamine,β-chloro-γ-(β'-chloroethylsulfonyl)propylamine,β-bromo-γ-(β'-chloroethylsulfonyl)propylamine,β-sulfato-γ-(β'-sulfatoethylsulfonyl)propylamine,bis[β-hydroxy-γ-(β'-chloroethylsulfonyl)propyl]amine,bis[β-chloro-γ-(β'-chloroethylsulfonyl)propyl]amine,bis[β-sulfato-γ-(β'-sulfatoethylsulfonyl)propyl]amine,β-hydroxy-γ-(vinylsulfonyl)propylamine,β-[β'-(β"-chloroethylsulfonyl)ethoxy]ethylamine,4-(β-chloroethylsulfonyl)cyclohexylamine,4-(β-sulfatoethylsulfonyl)cyclohexylamine,4-(β-sulfatoethylsulfonyl)piperidine, 4-(vinylsulfonyl)piperidine,N'-[γ-(β'-chloroethylsulfonyl)propyl]piperazine,2-[β-(β'-chloroethylsulfonyl)ethyl]piperidine and3-[(β-sulfatoethylsulfonyl)methyl]piperidine.

Bivalent coupling components suitable for synthesizing those disazo dyesin which the bivalent coupling radical is bonded to two diazo componentsof which one contains a fiber-reactive radical of the general formulaY--SO₂ --X¹ -- and the other contains a fiber-reactive radical of thegeneral formula (4) are for example resorcinol,5,5'-dihydroxy-7,7'-disulfo-2,2'-dinaphthylurea and in particular1-amino-8-naphthol-3,6-disulfonic acid and1-amino-8-naphthol-4,6-disulfonic acid.

The dyes conforming to the general formula (1) according to theinvention are suitable for use as fiber-reactive dyes for dyeing andprinting hydroxy-containing fibers, such as cellulose fiber materials,in particular cotton, but also synthetic or natural polyamide fiberssuch as wool. Suitable dyeing methods are the known dyeing and printingmethods for fiber-reactive dyes, in particular those for fiber-reactivedyes which contain a combination of fiber-reactive groups of thefluorotriazine and vinyl sulfone series. Such methods have beenrepeatedly described in the general and patent literature.

In particular, the dyes according to the invention are usable withadvantage in the cold pad-batch process, since they are notable for auniformly high yield of fixation. They can also be applied withadvantage by dyeing by the customary exhaust methods and also by theone-bath pad-steam processes, the two-bath pad-batch processes and thetwo-bath pad-steam processes. Equally, in printing they give uniformlyhigh yields of fixation, independently of the method of fixation, whichmay be effected for example by steaming or by dry heat. The dyeings andprints obtainable according to the invention are of high brilliance andcolor strength. They have good light fastness properties, even in thewet state, and good wet fastness properties, such as good fastness inthe 60° C. and 95° C. wash and good fastness to seawater, acid andalkaline perspiration and chlorinated water, but also a good peroxidefastness and fastness to gas fume fading. The dyes are also notable forimperviousness to atmospheric influences. Moreover, they produce gooddyeings on polyamide fiber material, such as wool, which have inparticular good light fastness and especially good wash and perspirationfastness properties. Furthermore, their buildup is good.

The Examples which follow serve to illustrate the invention. Parts andpercentages are by weight, unless otherwise stated. Parts by weight bearthe same relation to parts by volume as the kilogram to the liter. Thecompounds described in the Examples by means of formulae are shown inthe form of the free acids; in general, they are prepared and isolatedin the form of their sodium or potassium salts and used for dyeing inthe form of their salts. It is similarly possible to use the free acidstarting compounds and components mentioned in the Examples, inparticular the Table Examples, in the synthesis in that free acid formor in the form of their salts, preferably alkali metal salts.

The absorption maxima (λ_(max)) in the visible region reported for thecompounds according to the invention were determined on aqueoussolutions of their alkali metal salts. In the Table Examples, theλ_(max) values are given in brackets next to the hue; the wavelength isgiven in nm.

EXAMPLE 1

14.2 parts of cyanuric fluoride are gradually added over 5 minutes at 0°C. and a pH of 4.5 to a neutral solution of 31.9 parts of1-amino-3,6-disulfo-8-naphthol in 800 parts of water. 22.3 parts ofγ-(β'-chloroethylsulfonyl)propylamine hydrochloride are then added whilethe pH is maintained at 7 and the temperature at 5° to 15° C., andstirring is continued for some time thereafter. A further 22.3 parts ofthis propylamine hydrochloride are then added at 50°-55° C. and a pH of6.5 and stirring is continued at that temperature and a pH of 6.5 for afurther 4 hours. The batch then has added to it at 15° to 30° C. theaqueous hydrochloric acid solution of the diazonium salt of 51.1 partsof 1-sulfo-2-amino-6-(β-sulfatoethylsulfonyl)naphthalene, and thecoupling reaction is carried out at a pH of 6.

The resulting monoazo dye according to the invention is isolated fromthe synthesis solution by spray drying at a pH of 7. It has very gooddye properties and applied to the fiber materials mentioned in thedescription, in particular cotton, by the application and fixing methodscustomary for fiber-reactive dyes produces strong red dyeings. Writtenin the form of the free acid the dye has the formula: ##STR24##

EXAMPLE 2

The aqueous dye solution obtained according to Example 1 is stirred at0° to 5° C. and at a pH of 10.5 to 11.5 for about 4 hours and thenclarified in a conventional manner. The synthesized vinyl sulfone dye ofthe formula according to the invention is isolated in the form of analkali metal salt (the sodium salt) by spray drying at a pH between 5.5and 7. It likewise dyes fiber materials, such as cotton, in fast redshades. Written in the form of the free acid the dye has the formula:##STR25##

EXAMPLE 3

155.2 parts of cyanuric chloride are added with stirring to a suspensionof 255.2 parts of 1-amino-3,6-disulfo-8-naphthol in 1,440 parts of waterand 720 parts of ice while the pH is maintained at 1.7 to 2.2; the batchis subsequently stirred at 0° to 3° C. and the stated pH for about 4hours, then 204 parts of γ-(β'-hydroxyethylsulfonyl)propylaminehydrochloride are added and the second condensation reaction is carriedout at a pH of 7 and a temperature of 60° C. The third condensationreaction is carried out after the addition of a further 204 parts ofthis propylamine hydrochloride at a pH of 9 and a temperature of 80° to90° C. The batch then has added to it at 15° to 30° C. the aqueous,hydrochloric acid suspension of the diazonium salt of 411 parts of1-sulfo-2-amino-6-(β-sulfatoethylsulfonyl)naphthalene, and the couplingreaction takes place within that temperature range and at a pH of 7. Thesynthesis solution is then clarified and spray-dried. Theelectrolyte-containing product is added over an hour at not more than10° C. to a mixture of 800 parts by volume of sulfuric acid monohydrateand 424 parts by volume of 20% strength oleum. After about 2 hours theesterification ends at 10° C. The batch is discharged onto ice, andexcess sulfuric acid is neutralized by means of calcium carbonate. Thecalcium sulfate is filtered off with suction and washed with water. Thedye is isolated from the combined filtrates as an alkali metal salt byevaporating under reduced pressure at 60° C. or by spray drying. Writtenin the form of the free acid it has the formula: ##STR26## The dyeaccording to the invention dyes in particular cotton by the applicationand fixing methods customary for fiber-reactive dyes in deep, fastbluish red shades.

EXAMPLE 4

155.2 parts of cyanuric chloride are added with thorough stirring to asuspension of 255.2 parts of 1-amino-8-naphthol-4,6-disulfonic acid in1,400 parts of water and 720 parts of ice. The batch is stirred at 0° to3° C. and a pH of 1.7 to 2.2 for 4 hours. The synthesis of this primarycondensation product completed, the sulfuric acid diazonium saltsolution of the diazonium salt of 224.8 parts of4-(β-sulfatoethylsulfonyl)aniline in 750 parts of water is added, andthe coupling reaction is carried out at a pH of 4.0 to 4.5 and atemperature of above 5° C., which is gradually raised to 15°-20° C.Stirring is then continued for some time, and the batch is added to itwith 366.5 parts of γ-(β'-chloroethylsulfonyl)propylamine hydrochloride.The reaction is carried out at 0° to 3° C. and a pH of 7 for an hour andthen at a pH between 10.5 and 11.5 for 4 hours, in the course of whichthe β-chloroethylsulfonyl group changes into a vinylsulfonyl group.After the synthesis solution has been clarified, the resulting novel dyeof the formula (written in the form of the free acid) ##STR27## isisolated by spray drying. It has very good fiber-reactive dye propertiesand dyes for example cotton in fast yellowish red shades.

EXAMPLE 5

155.2 parts of cyanuric chloride are added to a suspension of 255.2parts of 1-amino-8-naphthol-3,6-disulfonic acid in 1,440 parts of waterand 720 parts of ice with stirring, and the reaction is carried out at apH of 1.7 to 2.2. After about 4 hours the sulfuric acid aqueous solutionof the diazonium salt of 224.8 parts of4-(β-sulfatoethylsulfonyl)aniline in about 750 parts of water is added,and the coupling reaction is carried out at a temperature of initially5° C. and later 15° to 20° C. and at a pH of 4.0 to 4.5. After stirringfor several hours the synthesis batch has added to it 480 parts ofβ-[β'-(β"-chloroethylsulfonyl)ethoxy]ethylamine hydrochloride, and thereaction is carried out at 0° to 3° C. and a pH of 7. After a reactiontime of 1 hour the pH is raised to 10.5-12, and the third condensationreaction is completed over 4 hours, in the course of which theβ-sulfatoethylsulfonyl group is converted into a vinylsulfonyl group.

The novel compound of the formula ##STR28## is isolated in the form ofan alkali metal salt in a conventional manner, for example by spraydrying. It has very good fiber-reactive dye properties and dyes forexample cotton in red shades.

EXAMPLE 6

A dichlorotriazinylamino monoazo compound prepared as described inExample 4 by reacting 1-amino-8-naphthol-4,6-disulfonic acid withcyanuric chloride and subsequent coupling with a diazonium salt of4-(β-sulfatoethylsulfonyl)aniline is reacted with twice the equivalentamount of N-[γ-(vinylsulfonyl)propyl]piperazine hydrochloride at 0° to5° C. initially for one hour at a pH of 7 and then for 4 hours at a pHof 10.5 to 12, in the course of which the β-sulfatoethylsulfonyl groupis converted into a vinylsulfonyl group. Isolation gives the novelcompound of the formula (written in the form of the free acid) ##STR29##which has very good fiber-reactive dye properties and dyes for examplecotton fast red shades.

EXAMPLE 7

A dichlorotriazinylamino monoazo compound prepared as per Example 5 inthe manner of the preceding Working Examples is reacted at 0° to 5° C.with twice the equivalent amount ofN-[β-(β'-chloroethylsulfonyl)ethyl]piperazine hydrochloride first at apH of 7 for one hour and then at a Ph between 11 and 12 for 4 hours, inthe course of which the β-chloroethylsulfonyl group is converted into avinylsulfonyl group. The novel fiber-reactive dye of the formula##STR30## is isolated in the form of an alkali metal salt in aconventional manner, for example by spray drying. It has very good dyeproperties and dyes for example cotton in red shades.

EXAMPLE 8

A dichlorotriazinyl(aminophenylpyrazolone)monoazo compound issynthesized in a conventional manner from cyanuric chloride,4-(β-sulfatoethylsulfonyl)aniline as diazo component and1-(2'-sulfo-4'-aminophenyl)-3-carboxy-5-pyrazolone. A pH of 6.8 to 7.2solution of 72.5 parts of this azo compound in 400 parts of water isadmixed at 0° C. with 47 parts of γ-(β'-chloroethylsulfonyl)propylaminehydrochloride. The condensation reactions are carried out at thistemperature first at a pH of 6.5 to 7 for one hour and then at a pHbetween 10.5 and 12 for 5 hours. The resulting monoazo compoundaccording to the invention is isolated by salting out with sodiumchloride or by spray drying. Written in the form of the free acid it hasthe formula ##STR31## and dyes for example cotton in strong yellowshades.

EXAMPLE 9

57.3 parts of the monoazo compound4-(1'-sulfo-6'-β-sulfatoethylsulfonylnaphth-2-ylazo)-3-acetylaminoanilineare reacted in a conventional manner in aqueous solution at a pH of 6.8to 7.2 and a temperature of 0° C. with 14.2 parts of cyanuric fluoride.After the acylation reaction has ended, 47 parts ofγ-(β'-chloroethylsulfonyl)propylamine hydrochloride are added, and thecondensation reactions are carried out first at 0° to 5° C. and a pH of7 for an hour and then at 50° to 55° C. and a pH of 6.5 for 5 hours. Theresulting dye according to the invention is isolated in the form of analkali metal salt. Written in the form of the free acid it has theformula ##STR32## and dyes for example cotton in strong, fast reddishyellow shades.

EXAMPLE 10

14.2 parts of cyanuric fluoride are gradually added at 0° C. and a pH of7 to a neutral aqueous solution of 56.2 parts of the monoazo compound2-(4'-methoxy-3'-β-sulfatoethylsulfonylphenylazo)-3-sulfo-6-amino-1-naphthol.After the acylation reaction has ended, 43 parts ofγ-(β-sulfatoethylsulfonyl)propylamine are added, and the condensationreactions are carried out at 0° to 5° C. and a pH of 7 for one hour andthen at 50° to 55° C. and a pH of 6.5 for 5 hours. The novel dye of theformula ##STR33## can be isolated in the form of an alkali metal salt bysalting out or spray drying. It dyes for example cotton by theapplication and fixing methods for fiber-reactive dyes in brilliantscarlet shades.

EXAMPLES 11 to 59

The Table Examples below describe further novel dyes conforming to thegeneral formula (A) ##STR34## with reference to their components (thediazo component D--NH₂, the coupling component H--K--NR.sup.α H, shownattached to triazinyl, and the amino radicals A and B). They can beprepared in a manner according to the invention, for example accordingto one of the above Working Examples, for example by reacting thecorresponding dihalotriazinylamino starting azo compound with thecorresponding amino compound conforming to the general formula (16) withor without simultaneous conversion of the radical Y¹ or Y² intovinylsulfonyl. They have very good fiber-reactive dye properties and dyefor example cotton in high color strength and good fastness propertiesin the hues indicated in the particular Table Example.

    __________________________________________________________________________    Dye of the formula (A)                                                        Ex.                                                                              Radical D--  Component H--K--NHR.sup.α                                                            Radicals A and B                                                                          Hue                                  __________________________________________________________________________    11 2-sulfo-4-(β-sulfato-                                                                 1-amino-3,6-disulfo-8-                                                                     γ-(β'-chloroethylsulfo-                                                        yellowish                               ethylsulfonyl)phenyl                                                                       naphthol     nyl)propylamine                                                                           red                                  12 2-sulfo-4-vinylsulfonyl-                                                                   1-amino-3,6-disulfo-8-                                                                     γ-(vinylsulfonyl)propyl-                                                            yellowish                               phenyl       naphthol     amino       red                                  13 2-carboxy-5-(β-sulfato-                                                               1-amino-3,6-disulfo-8-                                                                     γ-(β'-sulfatoethylsulfo-                                                       yellowish                               ethylsulfonyl)phenyl                                                                       naphthol     nyl)propylamino                                                                           red                                  14 3-(β-sulfatoethylsulfo-                                                               1-amino-3,6-disulfo-8-                                                                     γ-(β'-sulfatoethylsulfo-                                                       red                                     nyl)phenyl   naphthol     nyl)propylamino                                  15 3-vinylsulfonylphenyl                                                                      1-amino-3,6-disulfo-8-                                                                     γ-(vinylsulfonyl)propyl-                                                            red                                                  naphthol     amino                                            16 2-methoxy-5-(β-sulfato-                                                               1-amino-3,6-disulfo-8-                                                                     γ-(β-chloroethylsulfo-                                                         bluish red                              ethylsulfonyl)phenyl                                                                       naphthol     nyl)propylamino                                  17 2,5-dimethoxy-4-(β-sul-                                                               1-amino-3,6-disulfo-8-                                                                     γ-(β'-sulfaethylsulfo-                                                         bluish red                              fatoethylsulfonyl)phenyl                                                                   naphthol     nyl)propylamino                                  18 4-[N-(3'-β-sulfatoethyl-                                                              1-amino-3,6-disulfo-8-                                                                     γ-(β'-sulfaethylsulfo-                                                         red                                     sulfonyl)phenyl]carba-                                                                     naphthol     nyl)propylamino                                     moylphenyl                                                                 19 2-sulfo-5-[γ-(vinylsulfo-                                                            1-amino-3,6-disulfo-8-                                                                     γ-(vinylsulfonyl)propyl-                                                            yellowish                               nyl)butyrylamino]phenyl                                                                    naphthol     amino       red                                  20 4-sulfo-5-[γ-(vinylsulfo-                                                            1-amino-3,6-disulfo-8-                                                                     γ-(vinylsulfonyl)propyl-                                                            bluish red                              nyl)butyrylamino]phenyl                                                                    naphthol     amino                                            21 4-methoxy-3-(β-sulfato-                                                               1-amino-3,6-disulfo-8-                                                                     γ-(β'-chloroethylsulfo-                                                        bluish red                              ethylsulfonyl)phenyl                                                                       naphthol     nyl)propylamino                                  22 Copper complex with:                                                          2-hydroxy-5-(β-sulfato-                                                               1-amino-3,6-disulfo-8-                                                                      γ-(β'-sulfatoethylsulfo-                                                      violet                                  ethylsulfonyl)phenyl                                                                       naphthol     nyl)propylamino                                  23 Copper complex with:                                                          2-hydroxy-5-methoxy-4-                                                                     1-amino-3,6-disulfo-8-                                                                     γ-(β'-sulfatoethylsulfo-                                                       blue                                    β-sulfatoethylsulfonyl-                                                               naphthol     nyl)propylamino                                     phenyl                                                                     24 Copper complex with:                                                          2-hydroxy-6-sulfo-8-(β-                                                               1-amino-3,6-disulfo-8-                                                                     γ-(β'-chloroethylsulfo-                                                        blue                                    sulfatoethylsulfonyl)-                                                                     naphthol     nyl)propylamino                                     naphth-2-yl                                                                25 Copper complex with:                                                          2-hydroxy-5-(β-sulfato-                                                               3-(1'-amino-3',6'-di-                                                                      γ-(vinylsulfonyl)propyl-                                                            blue                                    ethylsulfonyl)phenyl                                                                       sulfo-8'-hydroxynaphth-                                                                    amino                                                            7'-yl)azo-6-sulfo-8-                                                          naphthol                                                      26 2-sulfo-6-(β-sulfato-                                                                 1-amino-4,6-disulfo-8-                                                                     γ-(β'-sulfatoethylsulfo-                                                       red                                     ethylsulfonyl)naphth-                                                                      naphthol     nyl)propylamino                                     2-yl                                                                       27 2-sulfo-vinylsulfonyl-                                                                     1-(2'-sulfo-4-amino-                                                                       β-[β'-(vinylsulfonyl)-                                                          yellow                                  phenyl       phenyl)-3-carboxy-5-                                                                       ethoxy]ethylamino                                                pyrazolone                                                    28 2-sulfo-6-(β-sulfato-                                                                 1-(2'-sulfo-4-amino-                                                                       γ-(β'-chloroethylsulfo-                                                        yellow                                  ethylsulfonyl)naphth-                                                                      phenyl)-3-carboxy-5-                                                                       nyl)propylamino                                     2-yl         pyrazolone                                                    29 4-[N-(3'-β-sulfatoethyl-                                                              1-(2'-sulfo-4-amino-                                                                       γ-(β'-sulfatoethylsulfo-                                                       yellow                                  sulfonyl)carbamoyl]phenyl                                                                  phenyl)-3-carboxy-5-                                                                       nyl)propylamino                                                  pyrazolone                                                    30 2-methoxy-5-methyl-4-(β-                                                              1-(2'-sulfo-4-amino-                                                                       γ-(β'-sulfatoethylsulfo-                                                       yellow                                  sulfatoethylsulfonyl)-                                                                     phenyl(-3-carboxy-5-                                                                       nyl)propylamino                                     phenyl       pyrazolone                                                    31 2,5-dimethoxy-4-(β-sul-                                                               1-(2'-sulfo-4'-amino-                                                                      γ-(β'-sulfatoethylsulfo-                                                       golden yellow                           fatoethylsulfonyl)phenyl                                                                   phenyl)-3-methyl-5-                                                                        nyl)propylamino                                                  pyrazolone                                                    32 2,5-dimethoxy-4-(β-sul-                                                               1-(2'-sulfo-4'-amino-                                                                      γ-(vinylsulfonyl)propyl-                                                            golden yellow                           fatoethylsulfonyl)phenyl                                                                   phenyl)-3-methyl-5-                                                                        amino                                                            pyrazolone                                                    33 Copper complex with:                                                          2-hydroxy-5-(β-sulfato-                                                               1-(2'-sulfo-4'-amino-                                                                      γ-(vinylsulfonyl)propyl-                                                            yellow brown                            ethylsulfonyl)phenyl                                                                       phenyl)-3-methyl-5-                                                                        amino                                                            pyrazolone                                                    34 Copper complex with:                                                          2-hydroxy-5-(β-sulfato-                                                               1-(2'-sulfo-4'-amino-                                                                      4-[γ-(vinylsulfonyl)-                                                               brown                                   ethylsulfonyl)phenyl                                                                       phenyl)-3-methyl-5-                                                                        propyl]piperazin-1-yl                                            pyrazolone                                                    35 4-(β-sulfatoethylsulfo-                                                               1-(2'-sulfo-5'-amino-                                                                      γ-(vinylsulfonyl)propyl-                                                            yellow                                  nyl)phenyl   phenyl)-3-carboxy-5-                                                                       amino                                                            pyrazodone                                                    36 2-sulfo-6-vinylsulfonyl-                                                                   1-(2'-sulfo-5'-amino-                                                                      γ-(vinylsulfonyl)propyl-                                                            yellow                                  naphth-2-yl  phenyl)-3-carboxy-5-                                                                       amino                                                            pyrazodone                                                    37 4-vinylsulfonylphenyl                                                                      1-(2',4'-disulfo-5'-                                                                       γ-(vinylsulfonyl)propyl-                                                            yellow                                               aminophenyl)-3-methyl-                                                                     amino                                                            5-pyrazolone                                                  38 1-sulfo-6-vinylsulfonyl-                                                                   1-(2',4'-disulfo-5'-                                                                       γ-(vinylsulfonyl)propyl-                                                            yellow                                  naphth-2-yl  aminophenyl)-3-methyl-                                                                     amino                                                            5-pyrazolone                                                  39 2-sulfo-4-(β-sulfato-                                                                 3-carbamoyl-4-methyl-1-                                                                    γ-(β-sulfatoethylsulfo-                                                        greenish                                ethylsulfonyl)phenyl                                                                       (β-aminoethyl)-2-hy-                                                                  nyl)propylamino                                                                           yellow                                               droxyhydroxypyrid-6-one                                       40 2-sulfo-4-(β-sulfato-                                                                 4-methyl-1-(γ-aminopro-                                                              γ-(β-sulfatoethylsulfo-                                                        greenish                                ethylsulfonyl)phenyl                                                                       pyl)-2-hydroxypyrid-6-                                                                     nyl)propylamino                                                                           yellow                                               one                                                           41 1-sulfo-6-(β-sulfato-                                                                 3-carbamoyl-4-methyl-1-                                                                    β-[β'-(β"-chloroethyl-                                                     greenish                                ethylsulfonyl)naphth-                                                                      (γ-aminopropyl)-2-hy-                                                                sulfonyl)ethoxy]ethyl-                                                                    yellow                                  2-yl         droxypyrid-6-one                                                                           amino                                            42 6-sulfo-8-(β-sulfato-                                                                 3-carbamoyl-4-methyl-1-                                                                    γ-(β'-sulfatoethylsulfo-                                                       greenish                                ethylsulfonyl)naphth-                                                                      (γ-aminopropyl)-2-hy-                                                                nyl)propylamino                                                                           yellow                                  2-yl         droxypyrid-6-one                                              43 1-sulfo-6-vinylsulfonyl-                                                                   3-sulfomethyl-4-methyl-                                                                    γ-(vinylsulfonyl)propyl-                                                            greenish                                naphth-2-yl  1-(β-aminoethyl)-2-                                                                   amino       yellow                                               hydroxypyrid-6-one                                            44 2-sulfo-5-γ-(vinylsulfo-                                                             3-carbamoyl-4-methyl-                                                                      γ-(vinylsulfonyl)propyl-                                                            greenish                                nyl)butyrylamidophenyl                                                                     1-(γ-aminopropyl)-2-                                                                 amino       yellow                                               hydroxypyrid-6-one                                            45 2-sulfo-5-γ-(vinylsulfo-                                                             3-sulfomethyl-4-methyl-                                                                    γ-(vinylsulfonyl)propyl-                                                            greenish                                nyl)butyrylamidophenyl                                                                     1-(γ-aminopropyl)-2-                                                                 amino       yellow                                               hydroxypyrid-6-one                                            46 4-(β-sulfatoethylsulfo-                                                               1-amino-3,6-disulfo-8-                                                                     γ-(β-thiosulfatoethyl-                                                         red                                     nyl)phenyl   naphthol     sulfonyl)propylamino                             47 1-sulfo-6-vinylsulfo-                                                                      2-sulfo-5-acetylamino-                                                                     γ-(vinylsulfonyl)propyl-                                                            reddish                                 nyl-naphth-2-yl                                                                            aniline      amino       yellow                               48 1-sulfo-6-(β-sulfato-                                                                 3-ureidoaniline                                                                            γ-(β'-sulfatoethylsulfo-                                                       reddish                                 ethylsulfonyl)naphth-     nyl)propylamino                                                                           yellow                                  2-yl                                                                       49 6-sulfo-8-(β-sulfato-                                                                 3-ureidoaniline                                                                            γ-(β'-sulfatoethylsulfo-                                                       reddish                                 ethylsulfonyl)naphth-     nyl)propylamino                                                                           yellow                                  2-yl                                                                       50 6-sulfo-8-(β-sulfato-                                                                 2-sulfo-5-acetylamino-                                                                     β-[β'-(β"-chloroethyl-                                                     reddish                                 ethylsulfonyl)naphth-                                                                      aniline      sulfonyl)ethoxy]ethyl-                                                                    yellow                                  2-yl                      amino                                            51 1-sulfo-6-(β-sulfato-                                                                 2-sulfo-5-acetylamino-                                                                     γ-(β'-chloroethylsulfo-                                                        reddish                                 ethylsulfonyl)naphth-                                                                      aniline      nyl)propylamino                                                                           yellow                                  2-yl                                                                       52 4-(β-sulfatoethylsulfo-                                                               1-amino-3,6-disulfo-8-                                                                     A: γ-(β'-chloroethyl-                                                          red                                     nyl)phenyl   naphthol     sulfonyl)propylamino                                                          B: 4-[γ-(β'-chloroethyl-                                           sulfonyl)propyl]-                                                             piperazin-1-yl                                   53 2-methoxy-5-(β-sulfato-                                                               3-amino-6-sulfo-8-                                                                         γ-(β'-sulfatoethylsulfo-                                                       scarlet                                 ethylsulfonyl)phenyl                                                                       naphthol     nyl)propylamino                                  54 2-methoxy-5-(β-sulfato-                                                               3-methylamino-6-sulfo-                                                                     γ-(β'-sulfatoethylsulfo-                                                       scarlet                                 ethylsulfonyl)phenyl                                                                       8-naphthol   nyl)propylamino                                  55 1-sulfo-6-(β-sulfato-                                                                 3-amino-6-sulfo-8-                                                                         γ-(β'-sulfatoethylsulfo-                                                       orange                                  ethylsulfonyl)naphth-                                                                      naphthol     nyl)propylamino                                     2-yl                                                                       56 6-sulfo-8-(β-sulfato-                                                                 3-amino-6-sulfo-8-                                                                         γ(β'-sulfatoethylsulfo-                                                        orange                                  ethylsulfonyl)naphth-                                                                      naphthol     nyl)propylamino                                     2-yl                                                                       57 1-sulfo-6-vinylsulfonyl-                                                                   3-methylamino-6-sulfo-                                                                     γ-(β'-vinylsulfonyl)-                                                          orange                                  naphth-2-yl  8-naphthol   propylamino                                      58 6-sulfo-8-vinylsulfonyl-                                                                   3-methylamino-6-sulfo-                                                                     4-(β-vinylsulfonylethyl-                                                             orange                                  naphth-2-yl  8-naphthol   piperazin-1-yl                                   59 4-methoxy-3-(β-sulfato-                                                               3-methylamino-6-sulfo-                                                                     γ-(β'-sulfatoethylsulfo-                                                       scarlet                                 ethylsulfonyl)phenyl                                                                       8-naphthol   nyl)propylamino                                  __________________________________________________________________________

EXAMPLE 60

56.2 parts of the monoazo compound4-(5'-amino-2'-sulfophenylazo)-1-((4"-β-sulfatoethylsulfonyl-phenyl)-3-methyl-5-pyrazoloneare reacted in aqueous solution at 0° to 3° C. and a pH between 1.7 and2.2 with 15.5 parts of cyanuric chloride. 40.8 parts ofγ-(β'-hydroxyethylsulfonyl)propylamine hydrochloride are then added, andthe first condensation reaction is carried out at pH 7 and 60° C. andthe second condensation reaction at pH 9 and 80°-90° C. The resultingβ-hydroxyethylsulfonyl-containing azo compound is salted out withpotassium chloride, isolated and dried. It is added over an hour at atemperature of not more than 10° C. to a mixture of 80 parts by volumeof sulfuric acid monohydrate and 42.4 parts of 20% strength oleum. Thebatch is subsequently stirred at 10° C. for about 2 hours and then addedto ice, the mixture is neutralized with calcium carbonate, filtered withsuction, and the calcium sulfate is washed with water. The combinedfiltrates are evaporated under reduced pressure. This gives the novelcompound of the formula ##STR35## in the form of an alkali metal salt.It has very good fiber-reactive dye properties and dyes for examplecotton in deep yellow shades.

EXAMPLES 61 TO 77

The Table Examples below describe further novel azo compounds conformingto the general formula (B) ##STR36## with reference to the discerniblecomponents. They can be prepared in a manner according to the invention,for example as described in Working Example 60, by reaction of thestarting compound cyanuric chloride or cyanuric fluoride, the aminocompound conforming to the general formula (16), the amino-containinganiline or naphthylamine diazo component conforming to the generalformula H₂ N--D--NH₂ and the corresponding coupling component H--K. Theyhave very good fiber-reactive dye properties and produce on the fibermaterials mentioned in the description, in particular on cotton, by theapplication and fixing methods customary for fiber-reactive dyes strongdyeings and prints having the hue indicated in the particular TableExample for cotton.

    __________________________________________________________________________    Azo dye of the formula (B)                                                    Ex.                                                                              Radical --D--N═N--                                                                   Radical --K  Radicals A and B                                                                          Hue                                    __________________________________________________________________________    61 2,4-disulfo-5-azophenyl                                                                  1-(4'-vinylsulfonyl-                                                                       γ-(vinylsulfonyl)propyl-                                                            yellow                                               phenyl)-3-methylpyrazol-                                                                   amino                                                            5-on-4-yl                                                       62 1-sulfo-2-azonaphth-5-                                                                   1-(4'-β-sulfatoethyl-                                                                 γ-(β'-sulfatoethylsulfo-                                                       yellow                                    methylenyl sulfonyl)-3-methyl-                                                                        nyl)propylamino                                                  pyrazol-5-on-4-yl                                               63 4-sulfo-3-azophenyl                                                                      2-[N-methyl-N-(β-sul-                                                                 γ-(β'-sulfatoethylsulfo-                                                       orange                                               fatoethylsulfonyl)]-                                                                       nyl)propylamino                                                  amino-6-sulfo-8-hydroxy-                                                      naphth-7-yl                                                     64 2,4-disulfo-5-azophenyl                                                                  2-[N-methyl-N-(β-sul-                                                                 γ-(vinylsulfonyl)propyl-                                                            orange                                               fatoethylsulfonyl)]-                                                                       amino                                                            amino-6-sulfo-8-hydroxy-                                                      naphth-7-yl                                                     65 4-sulfo-3-azophenyl                                                                      3-[3'-β-chloroethylsul-                                                               γ(β'-sulfatoethylsulfo-                                                        orange                                               fonyl)benzoylamino]-6-                                                                     nyl)propylamino                                                  sulfo-8-hydroxynaphth-                                                        7-yl                                                            66 1-sulfo-2-azonaphth-5-                                                                   3-[3'-β-chloroethylsul-                                                               γ-(β'-chloroethylsulfo-                                                        orange                                    methylenyl fonyl)benzoylamino]-6-                                                                     nyl)propylamino                                                  sulfo-8-hydroxynaphth-                                                        7-yl                                                            67 4-sulfo-3-azophenyl                                                                      3-[N'-(3'-β-chloroethyl-                                                              γ-(β'-sulfatoethylsulfo-                                                       orange                                               sulfonylphenyl)]-                                                                          nyl)propylamine                                                  ureido-6-sulfo-8-                                                             hydroxynaphth-7-yl                                              68 1-sulfo-2-azonaphth-5-                                                                   3-[N'-(3'-β-chloroethyl-                                                              γ-(β'-sulfatoethylsulfo-                                                       orange                                    methylen-yl                                                                              sulfonylphenyl)]-                                                                          nyl)propylamine                                                  ureido-6-sulfo-8-                                                             hydroxynaphth-7-yl                                              69 1-sulfo-2-azonaphth-5-                                                                   3-[ N'-(4'-β-sulfato-                                                                 γ-(β'-sulfatoethylsulfo-                                                       orange                                    methylen-yl                                                                              ethylsulfonylphenyl)]-                                                                     nyl)propylamine                                                  ureido-6-sulfo-8-                                                             hydroxynaphth-7-yl                                              70 2,4-disulfo-5-azophenyl                                                                  3-[N'-(3'-vinylsulfo-                                                                      γ-(vinylsulfonyl)propyl-                                                            orange                                               nylphenyl)]ureido-6-                                                                       amino                                                            sulfo-8-hydroxynaphth-                                                        7-yl                                                            71 4-sulfo-3-azophenyl                                                                      1-(3'-vinylsulfonyl-                                                                       γ-(vinylsulfonyl)propyl-                                                            yellowish                                            benzoylamino)-3,6-di-                                                                      amino       red                                                  sulfo-8-hydroxynaphth-                                                        7-yl                                                            72 4-sulfo-3-azophenyl                                                                      1-(4'-vinylsulfonyl-                                                                       γ-(vinylsulfonyl)propyl-                                                            yellowish                                            benzoylamino)-3,6-di-                                                                      amino       red                                                  sulfo-8-hydroxynaphth-                                                        7-yl                                                            73 4-sulfo-3-azophenyl                                                                      1-(3'-vinylsulfonyl-                                                                       γ-(vinylsulfonyl)propyl-                                                            yellowish                                            benzoylamino)-4,6-di-                                                                      amino       red                                                  sulfo-8-hydroxynaphth-                                                        7-yl                                                            74 3-sulfo-4-azophenyl                                                                      1-(3'-β-chloroethylsul-                                                               γ(β'-chloroethylsulfo-                                                         bluish                                               fonyl-benzoylamino)-3,6-                                                                   nyl)propylamino                                                                           red                                                  disulfo-8-hydroxy-                                                            naphth-7-yl                                                     75 1-sulfo-2-azonaphth-5                                                                    1-(3'-β-chloroethylsul-                                                               γ-(β'-sulfatoethylsulfo-                                                       bluish                                    methylenyl fonyl-benzoylamino)-3,6-                                                                   nyl)proplyamino                                                                           red                                                  disulfo-8-hydroxy-                                                            naphth-7-yl                                                     76 1-sulfo-2-azonaphth-5                                                                    1-(3'-vinylsulfonyl-                                                                       γ-(vinylsulfonyl)propyl-                                                            bluish                                    methylenyl benzoylamino)-3,6-                                                                         amino       red                                                  disulfo-8-hydroxy-                                                            naphth-7-yl                                                     77 3-sulfo-4-azophenyl                                                                      1-(4'-β-sulfatoethyl-                                                                 γ-(β'-sulfatoethylsulfo-                                                       yellow                                               sulfonylphenyl)-3-                                                                         nyl)propylamino                                                  methylpyrazol-5-on-                                                           4-yl                                                            __________________________________________________________________________

EXAMPLE 78

81.1 parts of the disazo compound1-amino-2-(4'-β-sulfatoethylsulfonylphenylazo)-7-(2"-sulfo-5"-aminophenylazo)-8-naphthol-3,6-disulfonicacid are reacted in aqueous solution at a pH of 7 and a temperature of0° to 3° C. with 14.2 parts of cyanuric fluoride. 47 parts ofγ-(β'-chloroethylsulfonyl)propylamine hydrochloride are then added, andthe condensation reactions are first carried out at 0° to 5° C. and a pHof 7 for one hour and then at 50° to 55° C. and a pH of 6.5 for 5 hours.The synthesized novel azo dye of the formula ##STR37## is isolated inthe form of an alkali metal salt by salting out with an electrolytesalt, such as sodium chloride or potassium chloride, or by spray drying.It has very good fiber-reactive dye properties and dyes for examplecotton by the customary application and fixing methods in deep, fastnavy shades.

EXAMPLES 79 TO 86

The Table Examples below describe further novel disazo dyes conformingto the general formulae (C) and (D) ##STR38## in terms of thediscernible components. They can be prepared in a manner according tothe invention, for example as described in Working Example 78, byreaction of the amino-containing disazo dye with a cyanuric halide, suchas cyanuric fluoride or cyanuric chloride, and the amino compoundconforming to the general formula (16).

They have very good fiber-reactive dye properties and produce on thefiber materials mentioned in the description, in particular on cotton,by the application and fixing methods customary for fiber-reactivedyeings strong dyes and prints having the hue on cotton indicated in theparticular Table Example.

    __________________________________________________________________________            Dye of the formulae (C) and (D)                                       Ex.                                                                              Formula                                                                            Radical D.sup.3                                                                          Radical D.sup.4                                                                          Radicals A and B                                                                           Hue                                __________________________________________________________________________    79 (C)  4-vinylsulfonylphenyl                                                                     ##STR39## β-[β'-(vinylsulfonyl)ethyl-                                         amino]ethylamino                                                                           navy                               80 (C)  2-bromo-4-vinylsulfo-                                                                    "          γ-(vinylsulfonyl)propyl-                                                             "                                          nylphenyl             amino                                           81 (D)  2-bromo-4-vinylsulfo- nylphenyl                                                           ##STR40## γ-(vinylsulfonyl)propyl- amino                                                       "                                  82 (D)  2-sulfo-5-[3'-(β-                                                                   "          γ-(β'-sulfatoethylsulfo-                                                        "                                          chloroethylsulfonyl)- nyl)propylamino                                         benzoylamino]phenyl                                                   83 (C)  2-sulfo-5-[3'-(β- chloroethylsulfonyl)- benzoylamino]phenyl                          ##STR41## γ-(vinylsulfonyl)propyl- amino                                                       "                                  84 (D)  2-sulfo-5-[γ-(β'- chloroethylsulfonyl)- butyrylamino]ph            enyl                                                                                      ##STR42## γ-(β '-chloroethylsulfonyl)-                                       propylamino  "                                  85 (C)  2-sulfo-5-[γ-(β'- chloroethylsulfonyl)- butyrylamino]ph            enyl                                                                                      ##STR43## γ-(β'-chloroethylsulfonyl)-                                        propylamino  "                                  86 (D)  4-vinylsulfonylphenyl                                                                     ##STR44## γ-(vinylsulfonyl)propyl- amino                                                       "                                  __________________________________________________________________________

EXAMPLES 87 TO 93

The Table Examples below describe further novel disazo dyes conformingto the general formula (E) ##STR45## in terms of the discerniblecomponents. They can be prepared in a manner according to the invention,for example as described in Working Example 78, by reaction of theamino-containing disazo dye with a cyanuric halide, such as cyanuricfluoride or cyanuric chloride, and the amino compound conforming to thegeneral formula (16).

They have very good fiber-reactive dye properties and produce on thefiber materials mentioned, in particular on cotton, by the applicationand fixing methods customary for fiber-reactive dyes strong dyeings andprints having the hue on cotton indicated in the particular TableExample.

    __________________________________________________________________________    Dye of the formula (E)                                                        Ex.                                                                              Radical D.sup.5 --                                                                    Radical --E--                                                                         Radical --N═N--K--NH--                                                                  Radicals A and B                                                                         Hue                               __________________________________________________________________________    87 6-sulfo-8-(β-                                                                    2'-methyl-5'-                                                                         7-azo-8-hydroxy-3,6-                                                                        γ-(β'-chloroethyl-                                                            blue                                 sulfatoethyl-                                                                         methoxyphen-                                                                          disulfonaphth-1-yl-                                                                         sulfonyl)propyl-                                sulfonyl)-                                                                            1',4'-ylene                                                                           amino         amino                                           naphth-2-yl                                                                88 1-sulfo-6-(β-                                                                    2'-methylphen-                                                                        7-azo-8-hydroxy-3,6-                                                                        γ-(vinylsulfonyl)-                                                                 blue                                 sulfatoethyl-                                                                         1',4'-ylene                                                                           disulfonaphth-1-yl-                                                                         propylamino                                     sulfonyl)-      amino                                                         naphth-2-yl                                                                89 4-methoxy-3-(β-                                                                  (6',7')-mono-                                                                         1-azo-(6,7)-mono-                                                                           γ-(β'-chloroethyl-                                                            brown                                sulfatoethyl-                                                                         sulfonaphth-                                                                          sulfonaphth-4-                                                                              sulfonyl)propylamino                            sulfonyl)phenyl                                                                       1',4'-ylene                                                                           ylamino                                                    90 2-methoxy-5-                                                                          (6',7')-mono-                                                                         1-azo-(6,7)-mono-                                                                           γ-(β'-sulfatoethyl-                                                           brown                                (β-sulfato-                                                                      sulfonaphth-                                                                          sulfonaphth-4-                                                                              sulfonyl)propyl-                                ethylsulfonyl)-                                                                       1',4'-ylene                                                                           ylamino       amino                                           phenyl                                                                     91 1-sulfo-6-(β-                                                                    (6',7')-mono-                                                                         1-azo-2-methylphen-                                                                         γ-(β'-sulfatoethyl-                                                           brown                                sulfatoethyl-                                                                         sulfonaphth-                                                                          4-ylamino     sulfonyl)propyl-                                sulfonyl)-                                                                            1',4'-ylene           amino                                           naphth-2-yl                                                                92 6-sulfo-8-(β-                                                                    (6',7')-mono-                                                                         1-azo-2-methylphen-                                                                         γ-(β'-sulfatoethyl-                                                           brown                                sulfatoethyl-                                                                         sulfonaphth-                                                                          4-ylamino     sulfonyl)propyl-                                sulfonyl)-                                                                            1',4'-ylene           amino                                           naphth-2-yl                                                                93 1-sulfo-6-(β-                                                                    2'-methyl-5'-                                                                         7-azo-8-hydroxy-3,6-                                                                        γ-(β'-sulfatoethyl-                                                           blue                                 sulfatoethyl-                                                                         methoxyphen-                                                                          disulfonaphth-1-yl-                                                                         sulfonyl)propyl-                                sulfonyl)-                                                                            1',4'-ylene                                                                           amino         amino                                           naphth-2-yl                                                                __________________________________________________________________________

We claim:
 1. A dye conforming to the general formula (5b) or (5c)

    (Y--SO.sub.2 --X.sup.1).sub.n --D.sup.1 --N=N--E.sup.1 --N=N).sub.v K*--Z(5b)

    Z--D*--N=N--E.sup.1 --N=N).sub.v K.sup.1 --X.sup.2 --SO.sub.2 --Y(5c)

where n is 1 or 2, Y is vinyl, β-sulfatoethyl, β-haloethyl,β-thiosulfatoethyl, β-phosphatoethyl or β-acetoxyethyl, X¹ is a directbond, alkylene of 1 to 4 carbon atoms or the bivalent radical of analkanoylamido group of 2 to 5 carbon atoms, D¹ is a phenylenesubstituted by substituents R² and R³ which have the followingmeanings:R² is hydrogen, methyl, ethyl, methoxy, ethoxy, alkanoyl of 2to 5 carbon atoms, cyano, carboxy, sulfo, alkoxycarbonyl of 2 to 5carbon atoms, carbamoyl, N-(C₁ -C₄)carbamoyl, fluorine, chlorine,bromine or trifluoromethyl, R³ is hydrogen, methyl, ethyl, methoxy,ethoxy, cyano, carboxy, sulfo, alkanoylamino of 2 to 5 carbon atoms,alkoxycarbonyl of 2 to 5 carbon atoms, carbamoyl, N-(C₁ -C₄)-carbamoyl,fluorine, chlorine, nitro, sulfamoyl, N-(C₁ -C₄ -alkyl)-sulfamoyl,alkylsulfonyl of 1 to 4 carbon atoms, phenylsulfonyl or phenoxy, E¹ is aradical of the general formula (7a), (7b), (7c), or (7d) ##STR46## whereR² and R³ are each as defined above,R⁴ is hydrogen, alkyl of 1 to 4carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine, alkanoylamino of2 to 5 carbon atoms, benzoylamino, ureido, N'-phenylureido,N'-alkylureido of 1 to 4 carbon atoms in the alkyl moiety,phenylsulfonyl or alkylsulfonyl of 1 to 4 carbon atoms, M is hydrogen oran alkali metal, m is 1 or 2, p is zero, 1 or 2, R⁸ is hydrogen, alkylof 1 to 4 carbon atoms, cyano, carboxy, carbalkoxy of 2 to 5 carbonatoms, carbamoyl or phenyl, v is zero or 1, --K*--Z of formula (5b), isa radical of the general formula (8a), (8e) or (8f) ##STR47## where R²,R³, p and M are each as defined above,V is a phenylene substituted by R²and R³ defined above or is a naphthylene unsubstituted or substituted by1 or 2 sulfo groups, Z is a radical of the general formula (4) ##STR48##where 2 substituents from the group consisting of sulfo, carboxy,methyl, ethyl, methoxy, ethoxy and chlorine, or a group of the generalformula --SO₂ -- Y² whereY² has one of the meanings specified above forY or is β-hydroxyethyl, Y² being identical to or different from Y, k iszero, 1 or 2, k* is zero, 1, 2, 3 or 4, X is together with the N-atomthe bivalent radical of a heterocyclic containing 1 or 2 alkylene groupsof 1 to 5 carbon atoms with or without 1 or 2 hetero atoms selected fromnitrogen and oxygen, Y¹ has one of the meanings specified above for Y,Y¹ being identical to or different from Y, and W is hydrogen, methyl,sulfomethyl, carboxymethyl, straight-chain or branched alkyl of 2 to 6carbon atoms unsubstituted or substituted by 1 or 2 substituents fromthe group consisting of methoxy, ethoxy, carboxy, sulfo, hydroxy andhalogen, unsubstituted or methyl-substituted cycloalkylene of 5 to 8carbon atoms, or phenyl unsubstituted or R.sup.α is hydrogen orstraight-chain or branched alkyl of 1 to 4 carbon atoms unsubstituted orsubstituted by carboxy, sulfo, cyano, hydroxy or chlorine, A is a groupof the general formula (2a) or (2b) ##STR49## where G is astraight-chain or branched alkylene of 1 to 6 carbon atoms, or is analkylene of 2 to 6 carbon atoms which is interrupted by 1 or 2 groupsselected from oxygen and --NH--, the alkylene moieties beingstraight-chain or branched, or is cycloalkylene of 5 to 8 carbon atoms,unsubstituted or substituted by methyl, R is hydrogen, chlorine,bromine, fluorine, hydroxy, sulfato, cyano, carboxy, carbamoyl,carbalkoxy of 2 to 5 carbon atoms, alkanoyloxy of 2 to 5 carbon atoms,benzoylamino unsubstituted or substituted by 1 to substituted bysubstituents from the group consisting of alkyl of 1 to 4 carbon atoms,alkoxy of 1 to 4 carbon atoms, carboxy, sulfo and halogen, and B has oneof the meanings specified for A, A and B having meanings identical to ordifferent from each other, R⁸ as defined above, R^(x) is hydrogen, alkylof 1 to 4 carbon atoms, or alkyl of 1 to 4 carbon atoms substituted byalkoxy of 1 to 4 carbon atoms or by cyano, R^(y) is hydrogen, sulfo,sulfoalkyl having an alkylene moiety of 1 to 4 carbon atoms, cyano orcarbamoyl, R^(z) is alkylene of 1 to 6 carbon atoms, phenyleneunsubstituted or substituted by substituents from the group consistingof methyl, ethyl, chlorine, carboxy and sulfo, or alkylenephenylenehaving 2 to 4 carbon atoms in the alkylene moiety, D* is a phenyleneradical unsubstituted or substituted by 1 or 2 substituents from thegroup consisting of hydrogen, methyl, ethyl, methoxy, bromine, chlorine,carboxy and sulfo, or is a naphthylene radical unsubstituted orsubstituted by 1 or 2 sulfo groups, K¹ is a radical of the generalformula (9a), (9b) or (9c), ##STR50## where M, p, V, R², R³ and R⁸ areeach as defined above and the hydroxy group in the formula (9a) is orthoto the free bond attached to the azo group, X² is a direct bond,alkylene of 1 to 4 carbon atoms or the bivalent radical of analkanoylamido group of 2 to 5 carbon atoms.
 2. A dye as claimed in claim1 conforming to the general formula (5b)

    (Y--SO.sub.2 --X.sup.1).sub.n --D.sup.1 --N=N--E.sup.1 --N=N).sub.v K*--Z(5b)

where Y X¹, D¹, E¹, v, --K*--Z and n are each as defined in claim
 1. 3.A dye as claimed in claim 2, wherein X¹ is a direct bond.
 4. A dye asclaimed in claim 1, conforming to the general formula (5c)

    Z--D*--N=N--E.sup.1 --N=N).sub.v K.sup.1 --X.sup.2 --SO.sub.2 --Y(5c)

where Z, D*, E¹, v, K¹, X² and Y are each as defined in claim
 1. 5. Adye as claimed in claim 4, wherein X² is a direct bond.
 6. A dye asclaimed in claim 1, wherein R.sup.α is hydrogen.
 7. A compound asclaimed in claim 1, wherein R.sup.α is methyl.
 8. A dye as claimed inclaim 1, wherein A is a group of the general formula (2a) having themeaning mentioned in claim
 1. 9. A dye as claimed in claim 8, wherein Wis hydrogen or methyl, R is hydrogen, k is zero and Y¹ is β-sulfatoethylor β-chloroethyl.
 10. A dye as claimed in claim 9, wherein G isn-propylene.
 11. A dye as claimed in claim 1, wherein B has the samemeaning as A.
 12. A dye as claimed in claim 1, wherein Y is vinyl orβ-sulfatoethyl.
 13. A dye as claimed in claim 1, wherein the group ofthe general formula (4) ##STR51## is a group of the general formula (4A)##STR52## where Y¹ is vinyl or β-sulfatoethyl, β-haloethyl,β-thiosulfatoethyl, β-phosphatoethyl or β-acetoxyethyl, and a is 2 or 3.14. A dye as claimed in claim 13, wherein a is
 3. 15. A dye as claimedin claim 13, wherein Y¹ is vinyl, β-chloroethyl or β-sulfatoethyl.
 16. Adye as claimed in claim 1, wherein Y¹ is vinyl, β-chloroethyl orβ-sulfatoethyl.
 17. A dye as claimed in claim 1, wherein X¹ and X² are adirect bond.
 18. A dye as claimed in claim 1, wherein G is a branchedalkylene of 2 to 4 carbon atoms.
 19. A dye as claimed in claim 1,wherein G is a branched alkylene having 2 to 3 carbon atoms.
 20. A dyeas claimed in claim 1, wherein R^(z) is an alkylene of 1 to 4 carbonatoms.
 21. A dye as claimed in claim 1, wherien n is 1.